logo

OR SEARCH CITATIONS

My Activity
Publications
CONTENT TYPES

Figure 1Loading Img
Download Hi-Res ImageDownload to MS-PowerPointCite This:J. Chem. Educ. 2001, 78, 9, 1266
RETURN TO ISSUEPREVArticleNEXT

Synthesis and Use of Jacobsen's Catalyst: Enantioselective Epoxidation in the Introductory Organic Laboratory

  • John Hanson
    John Hanson
    Department of Chemistry, The University of Puget Sound, Tacoma, WA 98416-0320
    More by John Hanson
Cite this: J. Chem. Educ. 2001, 78, 9, 1266
Publication Date (Web):September 1, 2001
https://doi.org/10.1021/ed078p1266
RIGHTS & PERMISSIONS
Article Views
12285
Altmetric
-
Citations
17
LEARN ABOUT THESE METRICS
PDF (106 KB)
Get e-Alerts
Supporting Info (6)»
SUBJECTS:

Abstract

Jacobsen's catalyst, N,N'-bis(3,5-di-tert-butylsalicylidene)-1,2-cyclohexanediaminomanganese(III) chloride, is a popular reagent for the enantioselective epoxidation of alkenes. This reagent is successfully prepared in three steps by beginning organic chemistry students. A mixture of 1,2-diaminocyclohexane isomers is purified and resolved by crystallization (and recrystallization) with L-tartaric acid; a diimine is formed between the resolved trans-1,2-diaminocyclohexane and 3,5-di-tert-butyl-2-hydroxybenzaldehyde to produce the Jacobsen ligand; and finally Jacobsen's catalyst is prepared from the ligand by treatment with manganese(II) acetate followed by oxidation with air. The students then use their Jacobsen catalyst to enantioselectively epoxidize one of the following alkenes: 1,2-dihydronaphthalene, styrene, or α-methylstyrene. After purifying their epoxides by flash chromatography, students determine the enantiopurity by GC using a chiral column. In this series of experiments students utilize a wide variety of laboratory techniques: running a reaction at reflux, aqueous workup with a separatory funnel, recrystallization, flash chromatography, TLC, polarimetry, IR and NMR spectroscopy, and chiral GC analysis. These labs also reinforce many important concepts related to chirality, stereochemistry, and optical activity.

KEYWORDS (Audience):
KEYWORDS (Domain):
KEYWORDS (Pedagogy):
KEYWORDS (Subject):

Cited By

This article is cited by 17 publications.

  1. Jacqueline Bennett . Synthesis of Fluorescent, Photochromic, and Thermochromic Imines in a Minute at Room Temperature. 2020,,, 113-128. https://doi.org/10.1021/bk-2020-1345.ch010
  2. Shelby L. Hooe, Arnold L. Rheingold, Charles W. Machan. Electrocatalytic Reduction of Dioxygen to Hydrogen Peroxide by a Molecular Manganese Complex with a Bipyridine-Containing Schiff Base Ligand. Journal of the American Chemical Society 2018, 140 (9) , 3232-3241. https://doi.org/10.1021/jacs.7b09027
  3. Jorge H. Torres King, Hong Wang, and Ellen J. Yezierski . Asymmetric Aldol Additions: A Guided-Inquiry Laboratory Activity on Catalysis. Journal of Chemical Education 2018, 95 (1) , 158-163. https://doi.org/10.1021/acs.jchemed.7b00147
  4. Homar Barcena, Abraham Tuachi, and Yuanzhuo Zhang . Teaching Green Chemistry with Epoxidized Soybean Oil. Journal of Chemical Education 2017, 94 (9) , 1314-1318. https://doi.org/10.1021/acs.jchemed.6b00672
  5. Edward M. Treadwell, Zhiqing Yan, and Xiao Xiao . Epoxidation with Possibilities: Discovering Stereochemistry in Organic Chemistry via Coupling Constants. Journal of Chemical Education 2017, 94 (5) , 640-643. https://doi.org/10.1021/acs.jchemed.6b00587
  6. King Kuok (Mimi) Hii, Henry S. Rzepa, and Edward H. Smith . Asymmetric Epoxidation: A Twinned Laboratory and Molecular Modeling Experiment for Upper-Level Organic Chemistry Students. Journal of Chemical Education 2015, 92 (8) , 1385-1389. https://doi.org/10.1021/ed500398e
  7. Elon A. Ison and Ana Ison . Synthesis of Well-Defined Copper N-Heterocyclic Carbene Complexes and Their Use as Catalysts for a “Click Reaction”: A Multistep Experiment That Emphasizes the Role of Catalysis in Green Chemistry. Journal of Chemical Education 2012, 89 (12) , 1575-1577. https://doi.org/10.1021/ed300243s
  8. John R. Miecznikowski, John P. Caradonna, Kathleen M. Foley, Daniel J. Kwiecien, George P. Lisi, and Anthony M. Martinez . Introduction to Homogenous Catalysis with Ruthenium-Catalyzed Oxidation of Alcohols: An Experiment for Undergraduate Advanced Inorganic Chemistry Students. Journal of Chemical Education 2011, 88 (5) , 657-661. https://doi.org/10.1021/ed1001575
  9. Kendrew K. W. Mak , Y. M. Lai , and Yuk-Hong Siu . Regiospecific Epoxidation of Carvone: A Discovery-Oriented Experiment for Understanding the Selectivity and Mechanism of Epoxidation Reactions. Journal of Chemical Education 2006, 83 (7) , 1058. https://doi.org/10.1021/ed083p1058
  10. Luigi Cavallo and, Heiko Jacobsen. Toward a Catalytic Cycle for the Mn−Salen Mediated Alkene Epoxidation:  A Computational Approach. Inorganic Chemistry 2004, 43 (6) , 2175-2182. https://doi.org/10.1021/ic0353615
  11. Mads Sondrup Møller, Morten Czochara Liljedahl, Vickie McKee, Christine J. McKenzie. Solid Phase Nitrosylation of Enantiomeric Cobalt(II) Complexes. Chemistry 2021, 3 (2) , 585-597. https://doi.org/10.3390/chemistry3020041
  12. Yulin Wang, Geoffrey I. N. Waterhouse, Lu Shang, Tierui Zhang. Electrocatalytic Oxygen Reduction to Hydrogen Peroxide: From Homogeneous to Heterogeneous Electrocatalysis. Advanced Energy Materials 2021, 11 (15) , 2003323. https://doi.org/10.1002/aenm.202003323
  13. Loyd D. Bastin, Manisha Nigam, Sam Martinus, James E. Maloney, Landon L. Benyack, Brendan Gainer. Synthesis of substituted N -phenylmaleimides and use in a Diels–Alder reaction: a green multi-step synthesis for an undergraduate organic chemistry laboratory. Green Chemistry Letters and Reviews 2019, 12 (2) , 127-135. https://doi.org/10.1080/17518253.2019.1609596
  14. Sabina-Alexandra Filimon, Dejan Petrovic, Jeroen Volbeda, Thomas Bannenberg, Peter G. Jones, Carl-Georg Freiherr von Richthofen, Thorsten Glaser, Matthias Tamm. 3d Metal Complexes Supported by a Bis(imidazolin-2-imino)pyridine Pincer Ligand - Synthesis, Structural Characterisation, and Magnetic Properties. European Journal of Inorganic Chemistry 2014, 2014 (35) , 5997-6012. https://doi.org/10.1002/ejic.201402804
  15. Séraphin Eyele-Mezui, Emilie Delahaye, Guillaume Rogez, Pierre Rabu. Functional Hybrid Materials Based on Layered Simple Hydroxide Hosts and Dicarboxylate Schiff Base Metal Complex Guests. European Journal of Inorganic Chemistry 2012, 2012 (32) , 5225-5238. https://doi.org/10.1002/ejic.201200695
  16. J. Krzystek, Joshua Telser. High frequency and field EPR spectroscopy of Mn(III) complexes in frozen solutions. Journal of Magnetic Resonance 2003, 162 (2) , 454-465. https://doi.org/10.1016/S1090-7807(03)00042-9
  17. Shanhong Yan, Dieter Klemm. Mild and efficient synthesis of 5,6-diamino-5,6-dideoxy-1,2-O-isopropylidene-3-O-methyl-β-l-idofuranose: precursor of the first carbohydrate-derived chiral Mn(III)–salen complex. Tetrahedron 2002, 58 (50) , 10065-10071. https://doi.org/10.1016/S0040-4020(02)01294-2

Pair your accounts.

Export articles to Mendeley

Get article recommendations from ACS based on references in your Mendeley library.

Pair your accounts.

Export articles to Mendeley

Get article recommendations from ACS based on references in your Mendeley library.

You’ve supercharged your research process with ACS and Mendeley!

STEP 1:
Click to create an ACS ID

Please note: If you switch to a different device, you may be asked to login again with only your ACS ID.

Please note: If you switch to a different device, you may be asked to login again with only your ACS ID.

Please note: If you switch to a different device, you may be asked to login again with only your ACS ID.

MENDELEY PAIRING EXPIRED
Your Mendeley pairing has expired. Please reconnect

This website uses cookies to improve your user experience. By continuing to use the site, you are accepting our use of cookies. Read the ACS privacy policy.

CONTINUE